Multimetallic complexes based on phosphine- and phosphine oxide- appended p-hydroquinones

Presented here, is the work done with a series of binucleating ligands based on phosphine and phosphine oxide appended p-hydroquinones and their reactions towards various metals sources. The long term goal of the project was to produce coordination polymers that would have novel electronic, magnetic, and optical properties which would be of use in the field of molecular electronics. Binucleating ligands contained a p-hydroquinone motif in which various phosphine- and phosphine oxide substituents have been placed in the ortho position relative to each of the hydroxy position were synthesized. A previously published synthetic method for such lugands utilized n-BuLi to form a phenyl lithium intermediate which was quenched with chlorodiphenylphosphine. This technique was also used to produce a ligand with diisopropylphosphine groups. Phosphine ligands, containing the same structural motif, were also generated using LDA as the lithiating agent. This technique was found to be higher yielding. Phosphine chalcogenide ligands were accessed by further oxidizing the low valent phosphorous centers with either hydrogen peroxide or with elemental sulfur. These ligands were characterized using multinuclear NMR, low and high resolution mass spectroscopy, FTIR, and single crystal X-ray diffraction. Their electrochemical properties were explored with cyclic voltammetry. The phosphine appended ligands were used in the synthesis of a several bimetallic complexes. It was found that the ligands readily reacted with NiCp2 and NiCp*2, displacing one of the cyclopentadiene (Cp) or pentamethylcyclopentadiene (Cp*) rings. A cyclopentadiene complexes, containing diisopropylphine, was readily oxidized by[FeCp2]PF6 to give a NMR silent mixed valence complex. Cyclic voltammetry of these complexes showed a number of reversible waves with a large potential separation. The mixed valence compounds also showed a large absorbance band in the NIR region which was assigned to be an intervalence charge transfer. The cyclic voltammetry and NIR spectroscopy suggest that these systems are very capable of efficient metal-to-metal charge transfer. These complexes were characterized by multinuclear NMR, single crystal X-ray diffraction, UV/VIS-NIR spectroscopy and elemental analysis. The phosphine oxide ligands were reacted with a variety of different metal sources but limited success was gained in obtaining single crystals, allowing structural characterization of these compounds. Single crystals were obtained from products generated by reacting the diphenylphosphine oxide ligand with (Bipy)Cu(NO3)2 and Cu(NO3)2. In all cases the ligand had been further oxidized to a 2,5-dihydroxy-1,4-benzoquinone motif. In the reaction between the diphenylphosphine oxide ligand and (Bipy)Cu(NO3)2 it was found that the phosphine oxide moiety was involved with intermolecular coordination leading to the formation of a one-dimensional polymer composed of a series of bimetallic complexes tethered together. When NaSbF6 was present in the reaction with (Bipy)Cu(NO3)2 a unique tetrametallic complex was formed. Here the phospine oxide moiety was oriented so that two bimetallic complexes were bound together. If only Cu(NO3)2 was present, a two-dimensional polymeric sheet was formed where the ligand was present in two different coordination modes. The electronic properties of these complexes remained to be assessed.

Impact of copper mine tailings (stamp sand) on survival and development of aquatic organisms near Gay, Michigan

Heavy metal-rich copper mine tailings, called stamp sands, were dumped by mining companies directly into streams and along the Lake Superior shoreline, degrading Keweenaw Peninsula waterways. One of the largest disposal sites is near Gay, Michigan, where tailings have been moved along the shoreline by currents since mining ceased. As a result, the smallest sand particles have been washed into deeper water and are filling the interstitial spaces of Buffalo Reef, a critical lake trout spawning site. This research is the first to investigate if stamp sand is detrimental to survival and early development of eggs and larvae of lake sturgeon, lake trout, and Northern leopard frogs, and also examines if the presence of stamp sands influences substrate selection of earthworms. This study found that stamp sand had significantly larger mean particle sizes and irregular shapes compared to natural sand, and earthworms show a strong preference for natural substrate over any combination that included stamp sand. Additionally, copper analysis (Cu2+) of surface water over stamp sand and natural sand showed concentrations were significantly higher in stamp sand surface water (100 μg/L) compared to natural sand surface water (10 μg/L). Frog embryos had similar hatch success over both types of sand, but tadpoles reared over natural sand grew faster and had higher survival rates. Eggs of lake sturgeon showed similar hatch success and development over natural vs. stamp sand over 17 days, while lake trout eggs hatched earlier and developed faster when incubated over stamp sand, yet showed similar development over a 163 day period. Copper from stamp sand appears to impact amphibians more than fish species in this study. These results will help determine what impact stamp sand has on organisms found throughout the Keweenaw Peninsula which encounter the material at some point in their life history.

An Ecological and Chemical Assessment of Copper Contaminated Streams in the Keweenaw Peninsula

The copper mining boom in Michigan's Upper Peninsula ended in the mid-1960s, but the historical mining still affects the region to this day. Earlier studies conducted in the Keweenaw have shown that trace metals in the sediments negatively affect benthic macroinvertebrate populations. However, because the concentrations of trace metals that are observed to be toxic often differ significantly between the laboratory and the environment, a better method for determining toxic levels of trace metals in the natural environment is desirable in order to establish surface water quality guidelines that effectively protect aquatic life. There were four research objectives for this research project. First, to determine if trace-level concentrations of copper can result in detectable ecological impacts even in the presence of high dissolved organic carbon (DOC). Second, to determine if there is a "safe" concentration of total dissolved copper below which there is little to no ecological impairment. Third, to establish which streams in the Keweenaw Peninsula have been most impacted by elevated levels of total dissolved copper. Fourth, to use this information to evaluate revisions to the water quality criterion for copper that were recently proposed by the Michigan Department of Environmental Quality (MDEQ). In order to collect water quality and macroinvertebrate data, two sampling surveys of approximately 50 streams were completed in the spring and summer of 2012. Our findings demonstrate that negative ecological impacts can be detected even in the presence of high concentrations of DOC. The majority of surveyed streams showed evidence of total dissolved copper concentrations that were elevated above background levels. Our findings suggest that there are detectable negative impacts below the current water quality standard for copper in many Keweenaw streams. The diversity of benthic macroinvertebrates and the number of species present has been reduced as a result of exposure to copper. Additionally, the multimetric approach used by MDEQ is unable to detect copper impairment in local streams due to the use of several insensitive metrics. The proposed changes to the copper criterion would increase the amount of total dissolved copper allowable despite the fact that approximately 25% of streams sampled have aquatic chemistries that would leave them vulnerable to high levels of copper ions.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.